Chlorinated glycolide

ABSTRACT

Novel glycolide compounds which obtain chemiluminescent light when reacted with other necessary chemiluminescent reactants in the direct generation of light from chemical energy. By &#39;&#39;&#39;&#39;light&#39;&#39;&#39;&#39; as referred to herein is meant electromagnetic radiation at wavelengths falling between about 350 m Mu and about 1,000 m Mu .

United States Patent [191 aulding July 8, 1975 CHLORINATED GLYCULIDE[75] Inventor: Donald Roy Maulding, Branchburg Primary Exammer NOrmaMllestone Twp NJ Attorney, Agent, or Fzrm-Gordon L. Hart; Charles J.

lFickey [73] Assignee: American Cyanamid Company,

Stamford, Conn.

57 ABSTRACT [22] Filed: July 8, 1974 1 Novel glycolide compounds whichobtain chemilumi- [211 Appl' 7 nescent light when reacted with othernecessary che- Related US. Application Data miluminescent reactants inthe direct generation of [63] Continuation-impart 0f Ser. No. 248,768,April 28, light from chemical energy By light as referred to1972,aband0ned, herein is meant electromagnetic radiation at wavelengthsfalling between about 350 my, and about 1,000 [52] lU.S. Cll. 260/340.2;252/186; 252/188 i- [51] lint. U C07d 15/116 QC [58] Field of Search260/3402 i M Drawings Cll-TlLORTNATlED GlLYCOlLlllDlE This applicationis a continuation-in-part of application Ser. No. 248,768, filed Apr.28, 1972, and now abandoned.

The present invention relates to novel glycolide compounds which obtainchemiluminescent light when reacted with other necessarychemiluminescent reactants in the direct generation of light fromchemical energy. By light as referred to herein is meant electromagneticradiation at wavelengths falling between about 350 my. and about 1,000mu.

The art of generating light from chemical energy, i.e.,chemiluminescence, is continually in search of compositions which whenreacted substantially improve the intensity and lifetime of lightemission contrasted to known chemiluminescent compositions andreactions. Obviously, improved compositions are constantly in demand foruse as signal devices, for area illumination, etc.

Various compounds have been known and proposed in the past for obtainingchemiluminescent light. One group is based on the compoundtetramethylamino ethylene, reactive with oxygen. Such compounds must obviously be protected from air during storage.

Another group of compounds are derivatives of his aryl or heterocyclicderivatives of oxalic acid. These compounds react with a peroxide in thepresence of a solvent and a fluorescent compound to givechemiluminescent light. Although these oxalates are the best knownchemiluminescent systems, they have the disadvantage that the oxalatesare relatively expensive to prepare and are also relatively insoluble,thus limiting the amount of light obtainable from a given volume ofsolution.

lt is an object of this invention to obtain a chemiluminescentcomposition and a process employing said composition whereby a highefficiency may be obtained in the conversion of chemical energy intolight.

Another object is to obtain a chemiluminescent compound which produceslight over an extended period of time.

Another object of this invention is to obtain a chemiluminescentcomposition which attains light of substantially higher intensity andwith a greater degree of quantum efficiency than has been obtained withformer chemiluminescent compositions.

Another object of this invention is to obtain a chemiluminescentcomposition which may be employed to obtain light by a process which ismechanically simple and which is economically inexpensive.

Another object of this invention is to obtain a chemiluminescentreactant which is stable over a long period of time and which may besubsequently reacted to obtain chemiluminescent light.

Another object of this invention is to obtain a chemiluminescentreactant which when reacted will obtain chemiluminescent light by aprocess which is not hazardous.

Another object is to obtain a composition character ized by acontrollable (1) length of duration of chemiluminescence and (2)intensity of chemiluminescent illumination.

Another object is to obtain a process of regulating intensity andduration of chemiluminescence.

Other objects of this invention become apparent from the above andfollowing disclosure.

The term aryl group as used herein means a group which is derived froman aromatic compound by the removal of one or more atoms.

The term chemiluminescent reactant, as used herein, means (I) a mixturewhich will result in a chemiluminescent reaction when reacted with othernecessary reactants in the processes as disclosed herein, or (2) achemiluminescent composition.

The term fluorescent compound, as used herein, means a compound whichfluoresces in a chemiluminescent reaction, or a compound which producesa fluorescent compound in a chemiluminescent reaction.

The term chemiluminescent composition, as used herein, means a mixturewhich will result in chemiluminescence.

The term admixing, as used herein, means reacting or sufficientlybringing together component reactants to obtain a chemiluminescentreaction.

The term hydroperoxide compound as used herein is limited to peroxidecompounds having at least one l-lOO group, or a compound which uponreaction produces a compound with such a group.

The term peroxidic groups, as used herein, represents HOO, ROO, or

R is defined for the polycarbonyl compound below, while R is asubstituent such as alkyl, cycloalkyl, a-hydroxyalkyl, substitutedalkyl, for example.

The term diluent, as used herein, means a solvent or a vehicle whichwhen employed with a solvent does not cause insolubility.

The term peroxide compound, as used herein, also includes compoundswhich upon reaction produce the peroxide group.

The term hydrogen peroxide compound includes (1) hydrogen peroxide and(2) hydrogen peroxideproducing compounds.

I have now found a new class of compounds which react with a peroxide inthe presence of a solvent and a fluorescent compound to givechemiluminescent light.

These compounds are novel glycolide derivatives having the generalstructural formula:

wherein R represents halo-, i.e. bromo, chloro, and fluoro; alkyl, aryl,and hydrogen, provided at least two of the R substituents are alwayshalogroups.

Light emission is obtained by the reaction of a chlorinated glycolidewith hydrogen peroxide in the presence of a fluorescer. The lightintensity is increased substantially with increased substitution ofchloro groups. Ethyl benzoate can be used as solvent with tbutyl alcoholor 3-methyl-3-pentanol as cosolvents. A two phase system (9 parts/onepart by volume) of ethyl benzoate with 30% hydrogen peroxide provides anintensely bright system. With such fluorescers as 9,10-diphenylanthracene, perylene, 9, l 0-bis(phenyletained from anhydroushydrogen peroxide compounds such as perhydrate of urea (ureas peroxide),perhydrate of pyrophosphate (sodium pyrophosphate peroxide), perhydrateof histidine (histidine peroxide), sodium perborate, and the like. Stillanother form in which the H may be provided in the composition is thatof an anhydrous solution of H 0 in a suitable solvent such as an ether,an ester, an aromatic hydrocarbon, etc., of the type which would providea suitable diluent for the composition of this invention. Alternatively,the hydroperoxide employed in the composition or process could be anycompound having a hydroperoxidic group, such as hydroperoxide (ROOH) ora peroxy acid such as t-butyl hydroperoxide and. perbenzoic acid.Whenever hydrogen peroxide is contemplated tobe employed, any suitablecompound may be substituted which will produce hydrogen peroxide. I

The hydroperoxide concentration may range from about molar down to about10*, preferably about 2 molar down to about 10 molar. Thegenericcompound of this invention may be added as a solid or inadmixture with a suitable solid peroxide reactant or in a suitablediluent, or alternatively dissolved directly in a solution containingthe peroxide reactant.

Typical diluents within the purview of the instant discovery are thosethat do not readily react with a peroxide, such as hydrogen peroxide,and which do not readily react with the polycarbonyl compound or withthe rearranged polycarbonyl compound.

Although the addition of water tends to quenchthe production ofchemiluminescent light according to the present invention, water canserve as a partial diluent up to substantial major percentages (morethan 50%). The term water, as used herein, includes waterproducingcompounds such as hydrates.

Any one or more suitable diluents may be included with or in the placeof the water, as long as the peroxide employed is at least partiallysoluble in one or more of the diluent(s), such as, for example, at least1 gram of H 0 per liter of diluent. The following are typicalillustrative examples of the diluents or solventswhich may be singly orjointly employed: non-cyclic or cyclic ethers, such as diethyl ether,diamyl ether, diphenyl ether, anisole, tetrahydrofuran, dioxane, and thelike; esters such as ethyl acetate, propyl formate, amyl acetate,dimethyl phthalate, diethyl phthalate, methyl benzoate, and the like;aromatic hydrocarbons, such as benzene, xylene, toluene, .and the like,acids such as acetic or propionic acids.

The fluorescent compounds contemplated herein are numerous; and they maybe defined broadly as those which do not readily react on contact withthe peroxide employed in this invention, such as hydrogen peroxide;likewise, they do not readily react on contact with the generic compoundof this invention. Typical suitable fluorescent compounds for use in thepresent invention are those which have a spectral emission fallingbetween 330 millimicrons and 800 millimicrons and which are at leastpartially soluble in any of the above diluents, if such diluent isemployed. Among these are the conjugated polycyclic aromatic compoundshaving at least 3 fused rings; such as: anthracene, substitutedanthracene, benzanthracene, phenanthracene, substituted phenanthracene,naphthacene, substituted naphthacene, pentacene, substituted pentacene,and the like. Typical substituents for all of these are phenyl, loweralkyl, chlorine, bromine, cyano, alkoxy (C -C and other likesubstituents which do not interfere with the lighht-generating reactioncontemplated herein.

Numerous other fluorescent compounds having the properties givenhereinabove are well known in the art. Many of these are fully describedin Fluorescence and Phosphorescence, by Peter Pringsheim, IntersciencePublishers, Inc. New York, 1949. Other fluorescers are described in TheColour Index, Second Edition, Volume 2, The American Association ofTextile Chemists and Colorists, 1956, pp. 2907-2923. While only typicalfluorescent compounds are listed hereinabove, the person skilled intheart is fully aware of the fact that this invention is not so restrictedand that numerous other fluorescent compounds having similar propertiesare contemplated for use herein.

It hasbeen found that the molar (moles per liter of diluent)concentrations of the major components of the novel composition hereindescribed may vary considerably. It is only necessary that components bein sufficient concentration to obtain chemiluminescence. The molarconcentration of Glycolide normally is in the range of at least about 10molar, preferably in the range of at least about 10 to about 5 molar;the fluorescent compound is present in the range from about 10 to about5, preferably about 10 to about 10 molar; and the diluent must bepresent in a sufficient amount to form at least a partial solution ofthe reactants involved in the chemiluminescent reaction. There is noknown maximum limit on the concentration of the generic compound of thisinvention which may be employed in the reaction, and as discussed above,intense chemiluminescent light may be obtained by employment of the highconcentrations.

The ingredients of the composition of this invention may be admixed in asingle stage of admixing or in a sequence of steps of admixingingredients together or separately. Accordingly, alternativecompositions may be prepared which may be stored over a period of timeand which may be admixed with the final ingredient at a time when thechemiluminescent lighting is desired. For example, one such compositionwould be a composition which includes a generic compound of thisinvention and a fluorescent compound but which does not include aperoxide compound. Another alternative solid composition would be acomposition whichincludes a peroxide, but which does not include thefluorescent compound. Another alternative composition would be a solidcomposition which includes a solid generic compound of this inventionand a solid hydroperoxide compound, and which possibly additionallyincludes a solid fluorescent compound, but which does not include adiluent. Obviously, the preferred compositions which would be less thanall necessary components to produce a chemiluminescent light would be acomposition which would be substantially stable to a practical degreeover an extended period of time; otherwise, there would be no realadvantage in forming a chemiluminescent reactant to be employed in asubsequent chemiluminescent reaction.

The wavelength of the light emitted by chemiluminescence of thecompositions of this invention, i.e., the color of the light emitted,may be varied by the addition of any one or more energy transfer agents(fluorescers) such as the known fluorescent compounds discussed atlength above.

The wavelength of the light emitted by the composition of this inventionwill vary, depending upon the particular fluorescent component employedin the reaction.

Although in the process of obtaining chemiluminescent light according tothis invention, it is normally not necessary to employ a specific orderto sequence of steps in the adding of the individual ingredients of theinventive chemiluminescent composition, it has been found that thefluorescent component preferably should be already in the reactionmixture at the time of addition of the last component necessary to bringabout the chemical reaction and the concurrent release of chemicalenergy.

Additionally, it has been found that the superior intensity ofchemiluminescence is obtained when the final mixture producing theluminescence is maintained at a temperature of between about 40C. and100C., preferably between about 20C. and 50C., the luminescence ofapplicants process is not limited to these ranges and temperature is notcritical.

The lifetime and the intensity of the chemiluminescent light can beregulated by the use of certain regulators such as 1. By the addition ofweak bases to the chemiluminescent composition to increase intensity.Both the strength and the concentration of the base are critical forpurposes of exactness in regulation.

2. By the variation of hydroperoxide. Both the type and theconcentration of hydroperoxide are critical for the purposes ofexactness in regulation.

The following examples are intended to illustrate the present inventionand are in no way intended to limit the invention except as limited inthe appended claims.

EXAMPLE 1 Chlorination of Glycolide-To 11.6 g. (0.10 mole) of glycolideand 250 ml of refluxing chloroform in a Pyrex flask was added chlorinegas as the solution was irradiated with a GE. EH6 lamp. The addition ofchlorine was stopped after 6 hours and a yellow color persisted for anadditional 15 minutes. The solvent was removed 5 and the resulting thickoil was distilled. The analysis of the first fraction, b.p. l26128/21mm, wt. 2.9 g. (16%), IR, 1775 and 1,800 cm, was for the 2,5-dichlorogylcolide.

Anal. Calcd. for C l l Cl O C, 25.92; H, 1.08; Cl,

38.39. Found: C, 25.16; H, 0.98; Cl, 37.75.

The second fraction, b.p. 167168/21 mm, wt. 2.4 g (1 1%), 1R, 1775 and1,810 cm, was trichloroglycolide.

Anal. Calcd. for C l-lCl O C, 21.88, H, 0.48; Cl,

48.51. Found: C, 21.15; H, 0.65; Cl, 49.91.

The identification of the chlorinated species was determined as follows:

The infrared spectra of methyl mono and dichloroacetates show two peaksat 1,750 and 1,776 cm",

whereas methyl acetate and methyl trichloroacetate have single peaks at1,750 cm, respectively. The two peaks for the chlorinated esters are dueto rotational isomers, with the peak at the higher frequency (1,776 cm)corresponding to the isomer in which one chlorine atom is close to thecarbonyl oxygen atom.* Thus,

in the case of the chlorinated glycolides (l and 11), where thestereochemistry is fixed, a comparison of the infrared spectra of thedichloroglycolide (1775 and 1800 cm) and trichloroglycolide (1775 and1810 cm) indicates that the structure of the dichloroglycolide is Ila,since by analogy with l, the dichloroglycolide llb requires a peak at1810 cm.

*The Infra-red Spectra ofComp/ex Molecules, L. .l. Bellamy, John Wileyand Sons, New York, 1960.

TABLE 1 Chemiluminescence Tests for Glycolides with9,1O-Bis(phenylethynyl)anthracene' Chemiluminescence "'Concentration of9,l0-his(phcnylethynyl)anthraccne was 0.003 M. EB ethyl bcnzoatc and TBAt-butyl alcohol.

"In foot-lamberts cm.

I claim: 1. A compound of theformula:

UNITED STATES IATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENT NU. 3,894,050

DATED July 8, 1975 INVENTDMS) Donald Roy Maulding It is certified thaterror appears in the above-identified patent and that said LettersPatent is hereby cunected as shown below:

In Column 1, line 5, after "abandoned" insert which was a division ofapplication Ser. No. 886,04 5, filed Dec. 17, 1969 and now U.S. Pat. No.3,697,432.

In Column 1, insert the following statement as the second paragraph ofthe Specification:

-The invention herein described was made in the course of or under acontract (Contract No. N6092l-67-C-O2l4) or subcontract thereunder, (orgrant) with the Department of the Navy.

Signed and Sealed this Twenty-third Day of October, 1990 Attest:

HARRY F. MANBECK. JR.

Arresting Ofiicer Commissioner of Patents and Thulemarks

1. A COMPOUND OF THE FORMULA: